Furfural purification



K. H. HACHMUTH FURFURAL URIFICATION Filed Feb. y15, 1943' aaddlls warmem all!!! ,ERIE

June 6, 1944.

30ans 'wurm-land amivaua lfaienteddune Y or. Delaware 'Y application February inrosa.' serian No. 475.959

y s claims. (ci. 19e-.iai

This invention relates te iurfural purmeeuon and more particularly to the treatment of furfural which hasbeen employed as a selective' solvent in the extraction or concentration of unsaturated hydrocarbons from hydrocarbon streams containing the same, especial1yfoi`alis'team'distillation is lett behindin phatic -mono-olens and aliphatic conjugated 2 diolens" particularly butylenes and butadiene from respective'streams containing the same, whereby the furfural has become contaminated with polymer. This polymer comprises largely or consists essentially of polymerized Afuri'ural.

polymer, by a seriesof steps involvingsteam disthe polymer-containing iurfural whereby an overhead vapor is formed which comprises.4 polymer-free miur/al and water. The polymer.

being non-volatile even under thev conditie of 'the bot m o f the distillingzone where it may be withdrawnv continuously or allowed to accumulate.

Theeve'rhead vapors from the steani dis Apparently its formation takes place under the" influencent heat, pressure, moisture. hydrocarbons especially olens or diolen's; air or oxygen,

' and other conditions, and components present or encountered in the absorption and stripping zones. The concentration oi this polymer in the furfural continually increases with time of use until nnally it isso high that it becomes imperative to shut down the plant for cleaning or' "with-' `drawzil and discard of the furfural. Accumula- 6 4tion oi? this polymer is objectionable for a num- `ber oitV reasons. The polymer coats surfaces of f `the equipment interfering with heat transfer.

causing coking on heating coils or elements, plugging and other'diillculties. Also thepolymer reduces the. selectivity of the solvent.' The principal object o! the presentinventlon is -to provide a method of treating furl'ural' oo n- I taminated with Bpolyme'r'- in the manner above `de' s ':ribed in order to remove thepolym'er and recover pureffurfural for recycle step `are condensed whereupon theliquid co densateis allowed to undergo layer iormation. The upper layer ot'watcr containing dissolved 'furtural is withdrawn and recycled as such or after heating or after vaporiaation, to the steam distilling step'and thereby utilized as the source'4 of steam for carrying out this step. This prevents loss' 'of. valuable furfural from the system di'ssolved in the water which would otherwise be discarded; f 'I'heJ lower layer is composed of polymer-free s tnd'is'recycled to the extraction system -iorre-usetherein. s e By'proceeding in the 'manner .just outlined'. effective and 'eillcient recoveryof polymer-free furfural 'is 'accomplished with a minimumot loss of'iurfuralfrom the systemand the objectionable the solvent extraction system. Another obi is to eilect such A`piriication by steam distillation. Another ob-v 3.5/ the extraction unit. The recoveryor purlilca e :lect is to) prevent the loss of furfural from the purification system. Still another object is to type which allows continuous operation of the 40 i'urfural isbeing fed thereto. Peri m'ono-oleiln ordioleiln extractionland stripping hereinafter appeal.-

The-accompanying drawing portri'iys' more or 4 less diagrammatically one arrangement of equip:

l45 otsteam distillation, e condensation -oi' overhead.-

mentwhich has beendound -particularly suitable viorf carrying out of the present in'- vention. The .evaporatorand the; condensate accumulator and separator are shown in jcross- In accordance with thexpresent invention.

and recycle of water and furiural'laye tinued Just as before. imtil'most if no ,pplymertreeiuriural'is recovered from the iure fural which has been employed as a selectlv`e solf- .ventin the trumt 0f 31.191131 Y oleilns or conjugated able way, andthe lean turtural .feed andstcam;

hydrocarbons,

stripping the ricl are carried out con tinuously.A Either a part or all. 'as desired, of the@ leanstrlpped lfurtural is passed tothe rurfural recovery system forrenioval'of` polymer. and any 'f balance is passed directly,- without purification, to

to accumulation of polymer in an excessive or obf v Jeetionsbie amount, the' reed er the leen :unimi to the distilling 4zone is cut bil butv the, operations layer formation and separation and withdrawal ,of the furiural has been removed from the accumulated 5 0 "polymen desirably until the mixturein the tem of thedatuung eene contains' atleast-en I 'by vweight ot palmen v'Iiiereupon the polymerv ls withdrawn from the distilling noneln any sui)- speciilcally -dioleiln's and thereby contaminated with the 66 distan@ steps arerresumed as bfore,

are conprovided with a The steam for the steam distillation may be made in the steam dlstilling zone itself by providing heating elements such as an indirect coil in contact with the liquid phase therein, and

feeding the recycled water layerinto the bottom of the steam distillation zone whereby the re- Afeed containing the unsaturated hydrocarbon to be concentrated, say a C4 feed containing normal butane or butadiene, enters extractive distillation unit 2 via line I. The operation of unit 2 is fully described in my copending applications, Serial No. 454,312 filed August 10, 1942, and Serial No. 438,844 filed April 13, 1942. For purposes ofthe present description, it may be stated that this operation combins extraction with fractional distillation in afractionating column 2, the furfural being supplied continuously via line 5 from tank 5 to the top of the column and descending therein, and the hydrocarbon feed being vaporized upwardly countercurrently to the furfural, a reboiling arrangement 3 being provided at the bottom ofthe column. The residue gas leaves .via line 4.

The rich furfural passes via' line 1 'to stripping column 8 where the unsaturated hydrocarbon is driven off via line 9. The stripped lean furfural leaves via line I 0 whence a portion or all may be passed via line II tothe re-run unit. Any balance is passed via line I2 for recycle via line I3 and storage tank 6; l

The' reunit embodies an evaporator I4 kettle' heating element` I5 shown as a coil heated indirectly by steam. Coil I5 is preferably located suillciently above the bottom of evaporator I4 to allow accumulation of a very substantial amount of liquid in the kettle below the heating element, say "10 gallons in an evaporator three feet in diameter and six feet high. The purpose-of this is to insure that in the periodic polymer concentration step, hereinafter described, the polymer layer will not touch the heating element as in s doing it would cause coking' on -its surface.

In order to providev steam in the evaporator I4. water or steam, as desired, is fed into the kettle bymeans of line I6 the end of which may be perforated as indicated by the dotted line so as to disperse the incoming water or steam throughout thel kettle liquid. v l

A' polymer draw-01T line I1 is provided as shown, but as indicated herein, it is ordinarily not preferred to draw off polymer continuously as this would entail undue loss of'free furfural in admixture therewith. On the contrary, it is preferable to draw of! the polymer intermittently or pe-v riodically, allowingl it to accumulate in'the bottom of still I4 for a considerable period of time and then shutting oi! flow offeed in line Il to the re-run unit, cooking down. the polymer, that is, steam distilling most or all, of the free lfurfural therefrom, then draining off the polymer and resuming feed ilow in line I I.

The overhead vapors from evaporator I4, and

'partition 22.

desired.

usually consisting essentially of polymer-free furfural and water (although some butadiene dimer,

4vinyl cyclohexene-l, may be present in small amounts), leave via line I8 and are condensed in condenser I9. The liquid condensate passes via line 20 to accumulator-separator 2I into which it ilows on the right-hand side of overflow dam or In the separating compartment thus formed by we'ir 22, layer separation takes place continuously, the'water forming the upper layer and continuously overflowing over the Weir into the left-hand compartment whence it isA continuously removed via line 23 and the furfural layer continuously being withdrawn via line I3 and recycled to furfural surge tank 6.

The water layer made up of water saturated with furfural maybe passed via line 23 through heater or vaporizer 24 Where it may-be heated or converted to steam by means of high pressure o steam entering via line 25 and leaving via line 26. If desired, a small amount of steam may be fed into therecycle water stream by meansof line 21 or makeup water may be added in any other desired manner as by,means of line 30. Also if desired,.e1ement 24 may be partially oi' completely by-passed by means of line 28.` The recycle water phase, Whether steam'or liquid water or both, is fed into steam distilling zone I4 by means of line I6. Water may be removed from the re-run system by means 'of line 29 if Example 1 The re-run unit described above was operated as follows over a period of 172 hours. The following table gives an average hourly material balance during this operation. 'I'he gures in the rst four columns are`pounds per hour.

ADrawn ou intermittently (in this case on1y at end of run).

Allv external heat was supplied by the kettle element I5, using high pressure steam. The recycle water vaporizer 24 was not used. The unit was operated at atmospheric pressure.

A small amount of water was carried overhead in the furfural absorber 2 and in the fur# fural stripper 8. Consequently, make-up water was added at the re-run unit, as indicated in the table, by means of line 30.

Two liquid layers existed in the evaporator I4- almost continuously throughout the observed 172-hour period. The top layer was water satu-` rated With furfural. The lower layer was furfural and polymer with varying amounts of (water. This was dark brown to-black in color and was opaque. d

Atrtlie end of the' `T12-hour period,the polymer in the evaporator was concentrated and removed from the system as follows. Furfural feed 4vialine II was stopped and with the kettle elementV I5 still supplying all heat. the evaporation and water recycle operation was continued just as before'. After operating'in this manner for .20"hours', the concentration of furfural in the overhead `vapor had dropped from its normal .per cent of polymer.

value-of '31 weight per cent to 13 weight per cent. This indicated that the water layer in the evaporator was not any longer saturated with furfural andthat the polymer layer contained only a small quantity of furfural. Forty-two gallons of very viscous black material were then drawn off via line Il. This material analyzed 93 weight The polymer content of the furfural in the absorber-stripper system at the start and inish of 'the 172-hour period was `0.7 and 0.33 weight per cent, respectively. With 2500 gallons of furfral in the system, the polymer reduction amounted to 37 pounds. Total polymer removed during the 172-hour run was 400 pounds. Therefore, 313 pounds of polymer were formed in 172 hours, or 1.82 pounds per hour. The rate of furfural feed to the absorber was 1200 gallons per hour.

Therefore, during the run, the polymer forma-- tion rate was .0165 weight per cent of the furfural rate to the furfural absorber.

Example 2 recycle stream, afterpassing through the vapor- Y izer 24, had a temperature of 270 F.

While results were very satisfactory, it is preferred to use kettle heating element I5 in conjunction with vaporizer 24, the supply of steam to coil I5 being automatically controlled by a liquid-vapor interfacial lever controller applied to evaporator I4 for the purpose of actuating ay The process of the present invention can be operated either under moderate pressures or under a vacuum as desired. However, it will usually be desirable to operate at, atmospheric or a slight positive pressure to prevent the entry of air into the system. The presence of air (oxygen) pro,- motes furfural polymerization and so is objectionable. 4

This application is a continuation-in-part of my prior and copending application, Serial No. 460,874'led October 5, 1942.

I claim 1. The process of recovering polymer-free furfural from strippedl lean furfural which has been employed as a selective solvent in the extraction of aliphatic unsaturated hydrocarbons from hydrocarbon mixtures containing the same and has thereby` become contaminated with polymer, which comprises steam distilling said polymercontaminated furfural and thereby driving overhead vapors of polymer-free furfural and water and forming a residual bottom product of polymer, removing said overhead vapors of polymerfree furfural and water, condensing said overhead vapors, causing the'liquid condensate to form into an upper layer of water containing dissolved furiural and a lower layer of polymer-free furfural, withdrawing `said lower layer of poly- .mer-free furfural for recycle to the extraction system, withdrawing said upper layer of water containing dissolved furfural, and employing said water containing dissolved furfural as the source of steam for said steam distilling step.

2. A process for the separation of aliphatic unsaturated hydrocarbons comprising extracting said hydrocarbon from a stream containing the same by means of furfural in an absorption zone, introducing the furfural rich in said hydrocarbon to a stripping zone and there stripping said hydrocarbon, withdrawing lean furfural from said stripping zone, said lean furfural being contaminated with polymer during said extracting and stripping steps, steam distilling at least a portion of saidlean furfural, removing overhead vapors of polymer-free furfural and water and leaving the polymer behind, condensing said overhead vapors, causing theliquid condensate to form into an upper layer of water containing dissolved furfural and a lower layer of polymer-free furfural, withdrawing said polymer-free furfural and recycling same to said extracting step, withdrawing said water containing dissolved furfural,

'and recycling said water containing dissolved furfural and vaporizing same as the source of steam for said steam distilling step.

3. The process of claim 2 in which said extracting and stripping steps are carried out continuously, and said steam distillingstep is carried out batchwise, and additionally including the steps of allowing the polymer to accumulate in the bottom of the steam distilling zone while the polymer-containing lean furfural is being fed thereto, periodically discontinuing said feed while continuing to carry out steam distillation of the polymer-furfural mix'ture in the bottom ofthe distillation zone, condensation of overhead, layer separation, and water and furfural withdrawal and recycle steps, until the mixture in said bottom contains atleast by weight of polymer, and then withdrawing said bottom mixture from said distillingl zone and resuming said feed to said steam distilling zone and steam distilling said feed as before. f

4. The process of claim 1A in which said recycled water containing furfural is vaporized in a separate zone apart from said steam distilling zone and the resulting steam is introduced directlyl into said steam distilling zone as the steam for said steam distilling step.

5. The process of claim 1 in which heat is supplied to `said steam distilling zone by circulating a heat carrying medium in indirect heat exchange with the liquid in said zone and said recycled water containing dissolved furfural is supplied in liquidphase to said zone and is vaporized thereby.

6. The process of claim 1 in which heat is supplied tc said steam distilling zone both by vaporization of said recycled water containing furfural in a separate zone and direct introduction of the resulting steam into said steam distilling zone and by circulating a heat carrying medium in indirect heat exchange with the liquid in said steam distilling zone.

. KARL H. HACHMUTH. 

